EP0435240B1 - Composés cristal liquides - Google Patents

Composés cristal liquides Download PDF

Info

Publication number
EP0435240B1
EP0435240B1 EP90125450A EP90125450A EP0435240B1 EP 0435240 B1 EP0435240 B1 EP 0435240B1 EP 90125450 A EP90125450 A EP 90125450A EP 90125450 A EP90125450 A EP 90125450A EP 0435240 B1 EP0435240 B1 EP 0435240B1
Authority
EP
European Patent Office
Prior art keywords
liquid crystal
crystal compound
group
trifluoro
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90125450A
Other languages
German (de)
English (en)
Other versions
EP0435240A3 (en
EP0435240A2 (fr
Inventor
Yoshiichi C/O Showa Shell Sekiyu K.K. Suzuki
Shigenori C/O Showa Shell Sekiyu K.K. Sakuma
Noriko C/O Showa Shell Sekiyu K.K. Yamakawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Shell Sekiyu KK
Original Assignee
Showa Shell Sekiyu KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Shell Sekiyu KK filed Critical Showa Shell Sekiyu KK
Publication of EP0435240A2 publication Critical patent/EP0435240A2/fr
Publication of EP0435240A3 publication Critical patent/EP0435240A3/en
Application granted granted Critical
Publication of EP0435240B1 publication Critical patent/EP0435240B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0266—Antiferroelectrics
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/90—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with esterified hydroxyl and carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom

Definitions

  • This invention relates to a novel halogen-containing liquid crystal compound comprising an ester or ether of an optically active halogen-containing alcohol.
  • liquid crystal compounds of this invention are ferroelectric liquid crystal compounds exhibiting bistable states, and furthermore, the liquid crystal compounds of this invention (those wherein the haloalkyl group thereof is CF3 or C2F5) are ferroelectric liquid crystal compounds of novel type which exhibit three stable (tristable) states.
  • Electro-optic devices using liquid crystals which have been developed and put into practical use to date include those using nematic liquid crystals, such as a DSM mode, a TN mode, a G-H mode, and an STN mode.
  • nematic liquid crystals such as a DSM mode, a TN mode, a G-H mode, and an STN mode.
  • nematic liquid crystals have a very slow electro-optic response and require a switching time from several milliseconds to several tens of milliseconds and are thus limited in their range of application.
  • the slow response of these elements using nematic liquid crystals is due to the fact that the torque of moving molecules, which is basically based on anisotropy of their dielectric constant, is not very high.
  • bistable liquid crystals have difficulty in reaching a mono-domain state in their Sc* phase without an applied voltage, i.e., in reaching an ideal molecular orientation state, and easily undergo defect or a molecular orientation disturbance called twist.
  • the threshold value (voltage at which luminance changes by a prescribed value) is low, dynamic driving is liable to suffer from a reduction in contrast or a reduction in the viewing angle.
  • bistable liquid crystals do not exhibit a hysteresis loop as shown in Fig. 1, but exhibit hysteresis as shown in Fig. 2 so that they have no memory effect. Therefore, it is necessary to continue applying a voltage of v3 as shown in Fig. 2 or continue applying a high frequency for the liquid crystal to maintain a stable response in the Sc* phase, which, in either case, results in a considerable energy consumption.
  • EP-A-0 332 392 discloses dioxane liquid crystal compounds showing tristable liquid crystal phase. These compounds comprise alkyl groups at each of the terminals thereof.
  • EP-A-0 330 491 discloses liquid crystal compounds which may also comprise alkyl groups at each of the terminals thereof. One terminal may alternatively represent an alkoxy group. These compounds show the tristable liquid crystal phase.
  • An object of this invention is to provide not only a novel liquid crystal compound which exhibits two states, but also a novel liquid crystal compound which exhibits stable three molecular orientation (tristable) states having a high light/shade contrast in the absence of an electric field, which has well defined threshold characteristics and a well defined hysteresis curve or loop as shown in Fig. 3, which easily undergoes dynamic driving, and which can be used in liquid crystal electro-optic devices utilizing three states, which make it possible to obtain a high-speed response.
  • an object of this invention is to provide a novel bistable liquid crystal compound.
  • Another object of this invention is to provide a novel ferroelectric chiral smectic liquid crystal compound exhibiting three stable molecular orientation states which are entirely different from a chiral smectic C phase (Sc* phase) which is a conventional bistable state phase.
  • three states means stable three molecular orientation states as now explained.
  • a liquid crystal electro-optic device comprising a pair of electrode substrates with a prescribed gap therebetween and a ferroelectric liquid crystal sandwiched between the pair of substrates, the electrodes being connected to an electric power source so that voltage of triangular wave as shown in Fig. 4(A) can be applied thereto
  • the ferroelectric liquid crystal shows a first stable molecular orientation state as shown by numeral 2 of Fig. 4(D) when no electric field is applied thereto, a second stable molecular orientation state as shown by numeral 1 of Fig.
  • bistable liquid crystals do not have such three stable states, but exhibit states as shown in Figs. 4(B) and (C), respectively.
  • the above ferroelectric liquid crystals having three states (hereinafter sometimes referred to as tristable liquid crystals) according to the present invention produce striking effects when applied to Liquid crystal displays as compared with conventional nematic liquid crystals, as discussed.
  • the tristable ferroelectric liquid crystals of the present invention can be driven using a simple matrix display. Accordingly, a display element using the tristable ferroelectric liquid crystal can be produced in a simple manner, which makes it feasible to widen the display area and to reduce production costs, whereas conventional display elements require complicated production steps, encounter difficulty in widening the display area, and involve high production costs.
  • the present invention provides a liquid crystal compound represented by formula (I): wherein R1 represents an alkyl group having from 3 to 18 carbon atoms or an aralkyl group having from 7 to 18 carbon atoms; R2 represents an alkenyl group having from 2 to 18 (preferably from 3 to 14) carbon atoms; and having a double bond at the terminal; R3 represents CF3 or C2F5; X represents a single bond, -O-, -COO-, or -OCO-; Y represents -COO-, -OCO-, -CH2O-, or -OCH2-; A and B each represents a cyclic group each having 1 to 2 six-membered rings or naphthalene; and * indicates an optically active center.
  • R1 represents an alkyl group having from 3 to 18 carbon atoms or an aralkyl group having from 7 to 18 carbon atoms
  • R2 represents an alkenyl group having from 2 to 18 (preferably from 3 to 14)
  • Figures 1, 2, and 3 each shows the hysteresis curve or loop of an ideal bistable liquid crystal (which is not actually available), of a conventionally synthesized bistable liquid crystal, and of a tristable liquid crystal according to the present invention, respectively, in which the applied voltage is plotted as the abscissa and the transmittance (%) as the ordinate.
  • Figure 4(A) shows the triangular wave applied.
  • Figures 4(B), (C), and (D) each shows the electro-optic response of a commercially available nematic liquid crystal, a conventionally synthesized bistable liquid crystal, and a tristable liquid crystal according to the present invention, respectively, when the triangular wave of Fig. 4(A) is applied.
  • Figure 5 illustrates switching among the three states of a compound according to the present invention, in which (a) is the triangular voltage wave applied to the liquid crystal electro-optic element, (b) is the polarization inversion current; and (c) is the transmission change with the voltage (a).
  • Figure 6 shows an electro-clinic effect, in which (a) is an alternating voltage applied to a liquid crystal electro-optic element, and (b) shows the changes of transmittance with alternating voltage (a).
  • Figure 7 shows the tristable response waveform of the novel liquid crystal compound obtained in Example 1.
  • the triangular wave of straight line is an applied voltage.
  • the abscissa indicates time, and the ordinate indicates voltage for the triangular wave or transmittance (transmitted light intensity) (A.U.) for the curve.
  • Figure 8 shows the infrared absorption spectrum of the compound obtained in Example 1.
  • liquid crystal compounds represented by formula (I) preferred are those represented by formula: wherein R1 is as defined above; and x is an integer of from 1 to 12.
  • the compounds according to the present invention can be synthesized by starting with an optically active haloalkanol represented by formula (II): wherin R1 and R3 are as defined above.
  • optically active halogen-containing alcohols which can be preferably used in the present invention are 1,1,1-trifluoro-2-hexanol, 1,1,1-trifluoro-2-heptanol, 1,1,1-trifluoro-2-octanol, 1,1,1-trifluoro-2-nonanol, 1,1,1-trifluoro-2-decanol, 1,1,1-trifluoro-2-undecanol, 1,1,1-trifluoro-2-dodecanol, 1,1,1-trifluoro-2-tridecanol, 1,1,1-trifluoro-2-tetradecanol, 1,1,1-trifluoro-2-pentadecanol, 1,1,1-trifluoro-2-hexadecanol, 1,1,1-trifluoro-2-heptadecanol, and 1,1,1-trifluoro-2-octadecanol.
  • the starting alcohol represented by formula (II) can be obtained by asymmetric synthesis, optical resolution or the like technique.
  • processes using enzymes, yeasts or bacteria are effective.
  • the alcohol can be synthesized according to the reaction scheme illustrated below.
  • Ethyl trifluoroacetate and a Grignard reagent of an alkyl bromide are reacted to obtain a trifluoroalkyl ketone.
  • the ketone is reduced with sodium borohydride to obtain a 1-trifluoro-2-alkanol, which is then converted to an acetate ester.
  • the ester is stereo-selectively hydrolyzed in the presence of yeast or bacteria to obtain an optically active (R)- or (S)-compound of a 1-trifluoro-2-alkanol.
  • ethyl trifluoroacetate may be replaced with ethyl monofluoroacetate, ethyl difluoroacetate, ethyl pentafluoroacetate or ethyl trichloroacetate to obtain the corresponding optically active 1-haloalkyl-2-alkanol.
  • 4-Benzyloxybenzoic acid is converted to its acid chloride with a chlorinating reagent, e.g., thionyl chloride, which is then reacted with an (R)-(+)- or (S)-(-)-trifluoro-2-alkanol to obtain an ester.
  • a chlorinating reagent e.g., thionyl chloride
  • the ester is subjected to debenzylation, and the resulting phenol compound is reacted with a chloride of a 4-alkyloxy-4'-biphenylcarboxylic acid to obtain a desired compound.
  • liquid crystal compounds of the present invention can also be synthesized by dehydrating condensation between a 4-alkyl- or 4-alkoxy-4'-biphenylcarboxylic acid and a phenol derivative of an optically active haloalkanol in the presence of a condensing agent, e.g., dicyclohexylcarbodiimide (DCC).
  • a condensing agent e.g., dicyclohexylcarbodiimide (DCC).
  • liquid crystal compounds according to the present invention are shown below.
  • the methylene chloride phase was washed successively with diluted hydrochloric acid, water, an aqueous 1N sodium carbonate solution, and water and dried over anhydrous magnesium sulfate.
  • the solvent was removed by distillation under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography using silica gel to obtain 0.65 g of 1,1,1-trifluoro-2-octyl 4-benzyloxybenzoate.
  • Example 1 The liquid crystal compound obtained in Example 1 was filled, while in an isotropic phase, into a liquid crystal cell having a polyimide orientation film which had been subjected to a rubbing treatment on an ITO (indium tin oxide) electrode substrate (cell thickness: 2.7 »m).
  • ITO indium tin oxide
  • the resulting cell was slowly cooled at a cooling rate of 0.1 to 1.0°C/min to orientate the liquid crystal molecules in an S(3)* phase. Cooling was continued, and a triangular wave voltage of ⁇ 30 V and 10 Hz was applied to the cell at 90°C.
  • the cell was set between a pair of cross polarizing sheets in such a manner that the direction of the molecular longer axis with no voltage applied was in parallel with one of the polarizing sheets, and changes of transmitted light intensity due to the change of the triangular wave voltage were observed. As shown in Fig. 3, a well defined threshold voltage and a double hysteresis loop were revealed.
  • the novel liquid crystal compounds of the present invention all exhibit bistability. They also exhibit an electro-clinic effect as illustrated in Fig. 6.
  • the present invention makes conventionally available liquid crystal materials more useful and competent.
  • the compounds of the present invention have a CF3 group or a C2F5 group in the molecule thereof thereby exhibiting three stable states and can be utilized in a wide range of applications, such as in display devices and switching devices.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Claims (8)

  1. Composé de cristal liquide représenté par la formule (I) :
    Figure imgb0015
     dans laquelle R₁ représente un groupe alkyle ayant de 3 à 18 atomes de carbone ou un groupe aralkyle ayant de 7 à 18 atomes de carbone ; R₂ représente un groupe alcényle ayant de 2 à 18 atomes de carbone et contenant une double liaison à son extrémité ; R₃ représente CF₃ ou C₂F₅ ; X représente une liaison simple, -O-, -COO- ou -OCO- ; Y représente -COO-, -OCO-, -CH₂O- ou -OCH₂- ; A et B représentent chacun un groupe cyclique chacun des groupes cycliques ayant de 1 à 2 cycles à 6 maillons ou le naphtalène ; et * indique un centre optiquement actif.
  2. Composé de cristal liquide selon la revendication 1, dans lequel A et B sont choisis dans le groupe constitué d'un homocycle et des groupes hétérocycliques contenant de l'azote.
  3. Composé de cristal liquide selon la revendication 1, dans lequel R₂ représente un groupe alcényle ayant de 3 à 14 atomes de carbone et contenant une double liaison à son extrémité.
  4. Composé de cristal liquide selon la revendication 1, dans lequel X ou Y est une liaison ester, son sens est le même que le sens de l'ester fixé à gauche du carbone asymétrique constituant le centre optiquement actif.
  5. Composé de cristal liquide selon la revendication 1, dans lequel l'un des groupes A et B est un groupe biphényle et l'autre est un groupe phénylène.
  6. Composé de cristal liquide selon la revendication 1, dans lequel le groupe fluoroalkyle lié à l'atome de carbone asymétrique du centre optiquement actif est un groupe CF₃.
  7. Composé de cristal liquide selon la revendication 1, dans lequel ledit composé est représenté par la formule :
    Figure imgb0016
     dans laquelle R₁ est tel que défini à la revendication 1 ; et x est un nombre entier de 1 à 12.
  8. Composé de cristal liquide selon la revendication 1, qui présente une phase S*(3) dans laquelle le cristal liquide présente des états tristables d'orientation moléculaire.
EP90125450A 1989-12-27 1990-12-24 Composés cristal liquides Expired - Lifetime EP0435240B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP339481/89 1989-12-27
JP1339481A JP2822355B2 (ja) 1989-12-27 1989-12-27 三状態強誘電性条件で駆動させるための液晶電気光学素子

Publications (3)

Publication Number Publication Date
EP0435240A2 EP0435240A2 (fr) 1991-07-03
EP0435240A3 EP0435240A3 (en) 1991-09-18
EP0435240B1 true EP0435240B1 (fr) 1995-05-24

Family

ID=18327874

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90125450A Expired - Lifetime EP0435240B1 (fr) 1989-12-27 1990-12-24 Composés cristal liquides

Country Status (4)

Country Link
US (1) US5110498A (fr)
EP (1) EP0435240B1 (fr)
JP (1) JP2822355B2 (fr)
DE (1) DE69019703T2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY106839A (en) * 1989-08-18 1995-08-30 Mitsui Petrochemical Ind Carboxylate compounds, liquid crystal compositions containing said compounds and liquid crystal elements.
JPH05249435A (ja) * 1992-03-03 1993-09-28 Mitsubishi Gas Chem Co Inc 反強誘電性液晶素子
EP0571276A1 (fr) * 1992-05-20 1993-11-24 Showa Shell Sekiyu Kabushiki Kaisha Composé monomère liquide cristallin et composé polymère liquide cristallin modifié avec celui-ci
DE19509304A1 (de) * 1994-03-16 1995-09-21 Nippon Soken Antiferroelektrische Flüssigkristallzusammensetzung
JPH07278059A (ja) * 1994-04-08 1995-10-24 Nippon Soken Inc 反強誘電性液晶化合物
DE69522361T2 (de) 1994-04-18 2002-06-13 Nippon Soken Antiferroelektrische Flüssigkristallzusammentsetzung
JP3501866B2 (ja) * 1994-07-19 2004-03-02 株式会社日本自動車部品総合研究所 反強誘電性液晶組成物及びそれを用いた液晶表示素子
JP3052817B2 (ja) * 1995-12-28 2000-06-19 株式会社日本自動車部品総合研究所 反強誘電性液晶組成物
JPH1036844A (ja) * 1996-07-25 1998-02-10 Nippon Soken Inc 反強誘電性液晶組成物

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6127931A (ja) * 1984-07-16 1986-02-07 Asahi Glass Co Ltd トランス―エチレン誘導体化合物を含有する液晶組成物
EP0195974B1 (fr) * 1985-03-26 1989-11-29 F. Hoffmann-La Roche Ag Phénylisothiocyanates substitués par un radical alcényle et benzonitriles
DE3604462A1 (de) * 1986-02-13 1987-08-20 Merck Patent Gmbh Smektische fluessigkristalline phasen
EP0242716B1 (fr) * 1986-04-22 1991-03-20 F. Hoffmann-La Roche Ag Dérivés liquides cristallins de la pyridine
FR2612182B1 (fr) * 1987-03-12 1989-06-23 Centre Nat Rech Scient Esters phenyliques substitues utilisables comme cristaux liquides ferroelectriques, leur preparation et leur utilisation dans un dispositif de visualisation electro-optique
DE3709618A1 (de) * 1987-03-24 1988-10-06 Hoechst Ag Neue fluessigkristalline 5-phenylpyrimidin-derivate mit s(pfeil abwaerts)c(pfeil abwaerts)-oder s(pfeil abwaerts)c(pfeil abwaerts) -phase und verfahren zu ihrer herstellung
DE3709549A1 (de) * 1987-03-24 1988-10-06 Hoechst Ag Verwendung von 5-phenyl-pyrimidinderivaten als komponenten in smektischen fluessigkristallmischungen
JPH0745420B2 (ja) * 1987-07-24 1995-05-17 キヤノン株式会社 光学活性物質、その製造方法およびそれを含む液晶組成物
JP2660551B2 (ja) * 1987-07-28 1997-10-08 キヤノン株式会社 光学活性化合物及びそれを含む液晶組成物、液晶素子
US4921632A (en) * 1987-08-26 1990-05-01 Nec Corporation Liquid crystal compounds and compositions
US4917821A (en) * 1987-11-09 1990-04-17 Canon Kabushiki Kaisha Optically active mesomorphic compound and liquid crystal composition containing same
DE68906178T2 (de) * 1988-02-26 1993-11-11 Showa Shell Sekiyu Flüssigkristallverbindungen.
JPH0748735B2 (ja) * 1988-03-07 1995-05-24 東京電力株式会社 データ通信方式
EP0332392B1 (fr) * 1988-03-09 1994-12-07 Showa Shell Sekiyu Kabushiki Kaisha Composés liquides cristallins dérivés du dioxane

Also Published As

Publication number Publication date
JP2822355B2 (ja) 1998-11-11
JPH03197444A (ja) 1991-08-28
EP0435240A3 (en) 1991-09-18
US5110498A (en) 1992-05-05
DE69019703T2 (de) 1995-11-16
EP0435240A2 (fr) 1991-07-03
DE69019703D1 (de) 1995-06-29

Similar Documents

Publication Publication Date Title
EP0435240B1 (fr) Composés cristal liquides
US5938973A (en) Swallow-tailed compound and ferrielectric liquid crystal composition containing the same
US5184847A (en) Liquid crystal compounds
US6002042A (en) Liquid crystal compound
US5972243A (en) Ferrielectric liquid crystal compound
US5202054A (en) Liquid crystal compound
EP0878460B1 (fr) Composés racémiques et compositions de cristaux liquides anti-ferroélectrique les contenant
EP0418604B1 (fr) Composé de cristal liquide
JPH02131450A (ja) 液晶化合物
EP0413989B1 (fr) Composés de cristaux liquides
US5130050A (en) Liquid crystal compound
US5840209A (en) Optically active compound, liquid crystal compositions containing the optically active compound, and liquid crystal display device
JP3165473B2 (ja) チオフェン環を有する光学活性化合物
EP0844294A1 (fr) Composé racémique et composition liquide cristalline le contenant
US6128065A (en) Ferrielectric liquid crystal compound
EP0402233B1 (fr) Composés liquides cristallins
JP2895614B2 (ja) 液晶化合物
JP2933688B2 (ja) 液晶素子
JP2822356B2 (ja) 三状態強誘電性条件で駆動させるための液晶電気光学素子
JP2858427B2 (ja) 液晶化合物
EP0974636B1 (fr) Composé liquide cristallin ferriélectrique
JP2902398B2 (ja) 液晶化合物およびそれを用いた三安定状態間の光学応答を示す光学素子用液晶
JPH03123759A (ja) 液晶化合物
JPH09208956A (ja) フェリ誘電性液晶
JPH04235950A (ja) 三重結合を有する光学活性化合物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19920304

17Q First examination report despatched

Effective date: 19931013

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 69019703

Country of ref document: DE

Date of ref document: 19950629

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20011212

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20011227

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020109

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20021224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST